TW201343602A - Method of manufacturing PZT-based ferroelectric thin film - Google Patents
Method of manufacturing PZT-based ferroelectric thin film Download PDFInfo
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- TW201343602A TW201343602A TW102103139A TW102103139A TW201343602A TW 201343602 A TW201343602 A TW 201343602A TW 102103139 A TW102103139 A TW 102103139A TW 102103139 A TW102103139 A TW 102103139A TW 201343602 A TW201343602 A TW 201343602A
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- temperature
- stage
- pzt
- thin film
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- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000010408 film Substances 0.000 claims abstract description 83
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 11
- 238000005245 sintering Methods 0.000 claims description 217
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- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 claims description 2
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- 238000005280 amorphization Methods 0.000 description 1
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- 125000004429 atom Chemical group 0.000 description 1
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- RHHHGLCTQKINES-UHFFFAOYSA-M sodium;5-amino-2-methoxy-4-sulfobenzenesulfonate Chemical compound [Na+].COC1=CC(S(O)(=O)=O)=C(N)C=C1S([O-])(=O)=O RHHHGLCTQKINES-UHFFFAOYSA-M 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
- H01B3/10—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances metallic oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/06—Insulating conductors or cables
-
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Abstract
Description
本發明係關於使用化學溶液沉積法(以下簡稱CSD法;Chemical Solution Deposition)在基板上形成比較厚的膜之後,暫燒結正式燒結而製造鈦鋯酸鉛(以下簡稱PZT)系強介電質薄膜的方法。 The present invention relates to the use of a chemical solution deposition method (hereinafter referred to as CSD method; Chemical Solution Deposition) to form a relatively thick film on a substrate, and then temporarily sintered to form a lead zirconate titanate (hereinafter referred to as PZT) ferroelectric thin film. Methods.
近年來開始採用使用CSD法在基板上塗佈1次含PZT系強介電質組成物的溶液,形成一層平均100nm以上之比較厚的膜(厚膜)之PZT系強介電質薄膜的方法。因為必須要廉價地製造提高以PZT系強介電質薄膜為材料的壓電元件等的壓電特性,且結晶配向為(100)或(111)者。但是,前述一次塗佈所形成的較厚的膜,在製造過程容易在膜上發生龜裂而且膜密度有降低的傾向。 In recent years, a method of forming a PZT-based ferroelectric thin film having a relatively thick film (thick film) of an average thickness of 100 nm or more by applying a solution containing a PZT-based ferroelectric substance composition on a substrate by a CSD method has been used. . It is necessary to inexpensively manufacture piezoelectric characteristics of a piezoelectric element or the like which is made of a PZT-based ferroelectric thin film, and the crystal alignment is (100) or (111). However, the thick film formed by the above-described single application tends to be cracked on the film during the production process, and the film density tends to decrease.
在此,為了解決相關的不良情形,嘗試了在PZT系強介電質薄膜形成用組成物的溶液,添加供提高該溶液的黏性之用的丙二醇(propylene glycol)與乙醇等揮發性醇(例如參照專利文獻1)。此外,也嘗試了在PZT系強介電質薄膜形成用組成物的溶液,添加乾燥控制化學添加物 (DCCA;Drying Control Chemical Additive)或者結晶性細微粉(例如參照非專利文獻1)。進而,還嘗試在PZT系強介電質薄膜形成用組成物的溶液,添加供防止龜裂之緩和應力發生的PVP那樣的高分子而且藉由紅外線及/或來自電氣加熱器之熱而在一階段進行暫燒結,接著進行正式燒結(例如參照非專利文獻2)。 Here, in order to solve the related problem, a solution of a PZT-based ferroelectric thin film-forming composition was added, and propylene glycol such as propylene glycol and ethanol for increasing the viscosity of the solution was added ( For example, refer to Patent Document 1). In addition, a solution of a PZT-based ferroelectric thin film-forming composition was also added, and a dry control chemical additive was added. (DCCA; Drying Control Chemical Additive) or a crystalline fine powder (for example, refer to Non-Patent Document 1). Further, in the solution of the PZT-based ferroelectric thin film-forming composition, a polymer such as PVP for preventing the occurrence of cracking stress is added, and the infrared rays and/or the heat from the electric heater are used in one. The stage is temporarily sintered, followed by the main sintering (see, for example, Non-Patent Document 2).
[專利文獻1]日本專利特開2001-261338號公報(請求項1、段落[0018]~[0025]、表1) [Patent Document 1] Japanese Patent Laid-Open Publication No. 2001-261338 (Request Item 1, Paragraph [0018] to [0025], Table 1)
[非專利文獻1](股)技術情報協會發行「供達成目的之溶膠凝膠法之構造控制專技知識集」pp.60-63 [Non-Patent Document 1] (Shares) Technical Information Association issued "Building Control Expertise Knowledge Set for Sol-Gel Method for Achieving Purpose" pp. 60-63
[非專利文獻2]J Sol-Gel Technol(2008)47,pp.316-325 [Non-Patent Document 2] J Sol-Gel Technol (2008) 47, pp. 316-325
然而,考慮到工業化,本案發明人研究得知使用不含有害性很高的2-甲氧基乙醇的溶膠凝膠液,藉由1次塗佈PZT系強介電質薄膜形成用組成物形成厚膜,將此厚膜在一階段暫燒結,接著進行正式燒結的場合,所得到的PZT系強介電質薄膜不會成為緻密而且結晶配向性高的薄膜。接著,為了解決此課題,以對PZT系強介電質薄膜形成 用組成物之溶液加入一定的添加物為前提,本案的發明人等銳意檢討了在暫燒結階段使用紅外線之特徵的溫度模式之結果,終於完成了本發明。 However, in consideration of industrialization, the inventors of the present invention have studied to form a composition for forming a PZT-based ferroelectric thin film by using a sol-gel liquid containing no harmful 2-methoxyethanol. In the thick film, when the thick film is temporarily sintered in one stage and then subjected to the main sintering, the obtained PZT-based ferroelectric film does not become a dense film having high crystal orientation. Next, in order to solve this problem, a PZT-based ferroelectric thin film is formed. On the premise that a certain additive is added to the solution of the composition, the inventors of the present invention have carefully reviewed the results of the temperature mode in which the characteristics of infrared rays are used in the temporary sintering stage, and finally completed the present invention.
本發明之目的在於提供使用以溶膠凝膠法為代表的CSD法把平均一層為100nm以上的比較厚的膜之PZT系強介電質薄膜即使在1次完成塗佈、暫燒結、正式燒結而成膜,也不會在此PZT系強介電質薄膜發生龜裂而製造緻密且結晶配向性高的PZT系強介電質薄膜的成膜方法。 An object of the present invention is to provide a PZT-based ferroelectric thin film having a relatively thick film having an average thickness of 100 nm or more by a CSD method typified by a sol-gel method, even after one application, temporary sintering, and main sintering. In the film formation, a PZT-based ferroelectric thin film is not cracked, and a PZT-based ferroelectric thin film having a high density and a high crystallinity is formed.
本發明之第1觀點,係藉由在具有結晶面配向於(111)軸方向的下部電極的基板之前述下部電極上,塗佈PZT系強介電質薄膜形成用組成物,暫燒結後,正式燒結使結晶化而在前述下部電極上製造PZT系強介電質薄膜的方法,特徵為:前述暫燒結使用紅外線來進行,且至少包含由0℃~150℃之溫度範圍內的溫度(或室溫)起升溫而保持於200℃~350℃的溫度範圍內的溫度之第1保持階段,以及由前述第1保持階段的保持溫度升溫而保持於比前述第1保持階段的保持溫度更高的350℃~500℃之溫度範圍內的溫度的第2保持階段。 According to a first aspect of the present invention, a PZT-based ferroelectric thin film-forming composition is applied to the lower electrode of a substrate having a lower surface electrode having a crystal plane aligned in a (111)-axis direction, and after temporary sintering, A method of producing a PZT-based ferroelectric thin film on the lower electrode by formal sintering, wherein the temporary sintering is performed using infrared rays and includes at least a temperature ranging from 0 ° C to 150 ° C (or The room temperature is maintained at a temperature in the temperature range of 200 ° C to 350 ° C in the first holding phase, and the temperature in the first holding phase is raised to maintain the temperature higher than the holding temperature in the first holding phase. The second holding phase of the temperature in the temperature range of 350 ° C to 500 ° C.
本發明之第2觀點係根據第1觀點之發明,進而特徵為在直到前述第1保持階段為止之第1升溫速度為1℃/秒~10℃/秒的範圍內,前述第1保持階段起升溫直到前述 第2保持階段為止的第2升溫速度為1℃/秒~100℃/秒的範圍內。 According to a second aspect of the invention, the first temperature increase rate is from 1 ° C / sec to 10 ° C / sec in the first holding period, and the first holding period is Warm up until the foregoing The second temperature increase rate up to the second holding stage is in the range of 1 ° C / sec to 100 ° C / sec.
本發明之第3觀點,係根據第1或第2觀點之發明,特徵為前述正式燒結的保持溫度在550℃~800℃的溫度範圍內,直到前述保持溫度為止的升溫速度為2.5℃/秒~150℃/秒的範圍內。 According to a third aspect of the present invention, in the first aspect or the second aspect, the temperature of the main sintering is maintained in a temperature range of 550 ° C to 800 ° C, and the temperature rise rate up to the holding temperature is 2.5 ° C / sec. Within the range of ~150 ° C / sec.
本發明之第4觀點,係根據第1至第3觀點之發明,特徵為進而前述強介電質薄膜之膜厚在150nm~400nm的範圍內。 According to a fourth aspect of the present invention, in the fourth aspect of the invention, the film thickness of the ferroelectric thin film is in a range of from 150 nm to 400 nm.
本發明之第5觀點,特徵為具有根據第4觀點之PZT系強介電質薄膜的薄膜電晶體、電容器、IPD、DRAM記憶體用電容器、層積電容器、電晶體之閘極絕緣體、非易失性記憶體、焦電型紅外線檢測元件、壓電元件、光電元件、致動器、共振子、超音波馬達、或LC雜訊過濾元件之複合電子零件。 According to a fifth aspect of the present invention, there is provided a thin film transistor, a capacitor, an IPD, a DRAM memory capacitor, a laminated capacitor, a gate insulator of a transistor, and a PZT-based ferroelectric thin film according to the fourth aspect. A composite electronic component of a loss memory, a pyroelectric infrared detecting element, a piezoelectric element, a photovoltaic element, an actuator, a resonator, an ultrasonic motor, or an LC noise filter element.
在本發明之第1觀點的方法,如圖1及圖2所示,係藉由在具有結晶面配向於(111)軸方向的下部電極11的基板10之下部電極11上,塗佈PZT系強介電質薄膜形成用組成物12,暫燒結後,正式燒結使結晶化而在下部電極11上製造PZT系強介電質薄膜12的方法,特徵為:前述暫燒結使用紅外線來進行,且至少包含由0℃~150℃之溫度範圍內的溫度(或室溫)起升溫而保持於 200℃~350℃的溫度範圍內的溫度之第1保持階段14,以及由前述第1保持階段14的保持溫度升溫而保持於比前述第1保持階段14的保持溫度更高的350℃~500℃之溫度範圍內的溫度的第2保持階段16。如此,暫燒結時,設置包含第1保持階段14與第2保持階段16的複數之暫燒結溫度的保持階段(以下稱為「二段暫燒結」。另一方面,從前的保持階段為一段者稱為「一段暫燒結」),且把紅外線作為供暫燒結之用的熱源,所以PZT系強介電質薄膜之暫燒結時,熱分解、熱膨脹、熱收縮等之進行會變得平穩,所以可以防止龜裂而且可以提供緻密的PZT係強介電質薄膜之製造方法。 In the method of the first aspect of the present invention, as shown in FIG. 1 and FIG. 2, the PZT system is coated on the lower electrode 11 of the substrate 10 having the lower electrode 11 having the crystal plane aligned in the (111)-axis direction. The method for forming a PZT-based ferroelectric thin film 12 on the lower electrode 11 after the temporary sintering is performed by sintering the composition of the ferroelectric thin film forming composition 12, and the temporary sintering is performed by using infrared rays. Containing at least a temperature (or room temperature) in the temperature range of 0 ° C to 150 ° C to maintain The first holding phase 14 of the temperature in the temperature range of 200 ° C to 350 ° C and the temperature of the holding temperature of the first holding phase 14 are maintained at 350 ° C to 500 higher than the holding temperature of the first holding phase 14 The second holding phase 16 of the temperature within the temperature range of °C. In the temporary sintering, the holding period including the temporary sintering temperature of the plurality of the first holding stage 14 and the second holding stage 16 (hereinafter referred to as "two-stage temporary sintering" is provided. On the other hand, the previous holding stage is a part. It is called "a temporary sintering"), and infrared rays are used as a heat source for temporary sintering. Therefore, when the PZT-based ferroelectric thin film is temporarily sintered, thermal decomposition, thermal expansion, and heat shrinkage are stabilized. It can prevent cracking and can provide a method for producing a dense PZT-based ferroelectric thin film.
在本發明的第2觀點之方法,於暫燒結階段,藉由使室溫等之初期溫度起到第1保持階段14為止的第1升溫速度13,及接著的第1保持階段14起到第2保持階段16為止的第2升溫速度15分別為特定範圍,可以防止由於過度的升溫速度產生大的應力導致龜裂發生,防止急遽的熱分解或脫氣,可得更為緻密的PZT系強介電質薄膜。 According to the second aspect of the present invention, in the temporary sintering stage, the first temperature increase rate 13 from the initial temperature of the first holding stage 14 and the subsequent first holding stage 14 are performed. (2) The second temperature increase rate 15 up to the holding stage 16 is a specific range, and it is possible to prevent cracks from occurring due to excessive stress in an excessive temperature increase rate, and to prevent rapid thermal decomposition or degassing, thereby obtaining a denser PZT system. Dielectric film.
在本發明的第3觀點之方法,藉由使前述正式燒結的保持溫度在550℃~800℃的溫度範圍內,到前述保持溫度為止的升溫速度為2.5℃/秒~150℃/秒的範圍內,由第2保持階段16起直到正式燒結的保持溫度為止的升溫速度在特定範圍內,防止由於過度的升溫速度引起熱膨脹等導致龜裂發生,防止急遽的熱分解或脫氣,可得更為緻密的PZT系強介電質薄膜。 According to a third aspect of the present invention, in the temperature range of 550 ° C to 800 ° C in which the holding temperature of the main sintering is maintained, the temperature increase rate up to the holding temperature is in the range of 2.5 ° C / sec to 150 ° C / sec. In the inside, the temperature increase rate from the second holding stage 16 to the holding temperature of the main sintering is within a specific range, and cracking due to thermal expansion or the like due to excessive temperature increase rate is prevented, and rapid thermal decomposition or degassing is prevented. It is a dense PZT-based ferroelectric thin film.
10‧‧‧基板 10‧‧‧Substrate
11‧‧‧下部電極 11‧‧‧ lower electrode
12‧‧‧強介電質薄膜 12‧‧‧Digital dielectric film
13‧‧‧第1升溫速度 13‧‧‧1st heating rate
14‧‧‧第1保持溫度 14‧‧‧1st holding temperature
15‧‧‧第2升溫速度 15‧‧‧2nd heating rate
16‧‧‧第2保持溫度 16‧‧‧2nd holding temperature
17‧‧‧從前的升溫速度 17‧‧‧ Previous heating rate
18‧‧‧從前的保持溫度 18‧‧‧Previous temperature retention
圖1係概略顯示本發明的PZT系強介電質薄膜被配置於基板及下部電極的狀態之剖面圖。 Fig. 1 is a cross-sectional view schematically showing a state in which a PZT-based ferroelectric thin film of the present invention is disposed on a substrate and a lower electrode.
圖2係概略顯示相關於本發明之在二個處所有保持溫度區域的二段暫燒結相關的暫燒結的溫度變化圖(單點虛線),以及從前技術之在一個處所有保持溫度區域的一段暫燒結的溫度變化圖(實線)。 Figure 2 is a schematic view showing a temperature change diagram (single-dotted line) of the temporary sintering associated with the two-stage temporary sintering in all of the two holding temperature regions of the present invention, and a section of all the holding temperature regions of the prior art at one location Temporary sintering temperature change diagram (solid line).
圖3係依照相關於本發明的二段暫燒結的溫度變化圖,概略顯示3種斜率的第1升溫速度之實施例之圖。 Fig. 3 is a view schematically showing an example of a first temperature increase rate of three kinds of slopes in accordance with a temperature change diagram of two-stage temporary sintering according to the present invention.
圖4係顯示藉由相關於本發明的製造方法所製造的PZT系強介電質薄膜的SEM影像之剖面構造。 4 is a cross-sectional view showing an SEM image of a PZT-based ferroelectric thin film produced by the manufacturing method of the present invention.
圖5係顯示藉由先前技術製造的PZT系強介電質薄膜的根據SEM之剖面構造。 Fig. 5 is a cross-sectional view showing the structure according to SEM of a PZT-based ferroelectric thin film manufactured by the prior art.
圖6係藉由實施例6及比較例2所製作的PZT系強介電質薄膜的結晶之XRD圖。 Fig. 6 is an XRD pattern of crystals of a PZT-based ferroelectric thin film produced in Example 6 and Comparative Example 2.
以下將相關於PZT系強介電質薄膜之製造方法之本實施型態,分為<組成物準備階段>、<塗佈階段>、<暫燒結階段>及<正式燒結階段>進行說明。 Hereinafter, the present embodiment relating to the production method of the PZT-based ferroelectric thin film will be described in the following steps: "composition preparation stage", <coating stage>, <temporary sintering stage>, and <formal sintering stage>.
PZT系強介電質薄膜形成用組成物,以構成複合金屬 氧化物之用的原料成為提供所要的金屬原子比的比例的方式,藉由溶解於有機溶媒中的有機金屬化合物溶液來製造。又,「PZT系」強介電質薄膜包含除了PLZT、PMnZT、PNbZT等PZT以外的強介電質組成物。 PZT is a composition for forming a strong dielectric film to form a composite metal The raw material for the oxide is produced in such a manner as to provide a desired ratio of the atomic ratio of the metal to the organometallic compound solution dissolved in the organic solvent. Further, the "PZT-based" ferroelectric thin film contains a ferroelectric composition other than PZT such as PLZT, PMnZT, or PNbZT.
前述複合金屬氧化物的原料,以在Pb、La、Zr及Ti之各金屬元素,有機基透過其氧或氮原子而結合的化合物為適切的。例如可以例示由金屬烷氧化物(alkoxide)、金屬二醇錯合物、金屬三醇錯合物、金屬羧酸鹽、金屬β-二酮錯合物、金屬β-二酮酯錯合物、金屬β-亞氨酮錯合物、及金屬氨基錯合物構成的群所選出的1種或2種以上。特別適切的化合物,為金屬烷氧化物(alkoxide)、其部分加水分解物、有機酸鹽。其中,作為鉛化合物、鑭化合物,可以舉出醋酸鹽(醋酸鉛:Pb(OAc)2、醋酸鑭:La(OAc)3)、二異丙醇鉛:Pb(OiPr)2、三異丙醇鑭:La(OiPr)3等。做為鈦化合物,可以舉出四乙醇鈦:Ti(OEt)4、異丙醇鈦:Ti(OiPr)4、四正丁醇鈦:Ti(OiBu)4、四異丁醇鈦:Ti(OiBu)4、四t-丁醇鈦:Ti(OtBu)4、二甲氧基二異丙基鈦:Ti(OMe)2(OiPr)2等烷氧化物(alkoxide)。作為鋯化合物,與前述鈦化合物同樣以烷氧化物(alkoxide)類為佳。金屬烷氧化物直接使用亦可,為了促進分解於該部分使用加水分解物亦可。 The raw material of the composite metal oxide is suitable for a compound in which a metal element of Pb, La, Zr and Ti is bonded to an organic group through an oxygen or nitrogen atom. For example, a metal alkoxide, a metal diol complex, a metal triol complex, a metal carboxylate, a metal β-diketone complex, a metal β-diketone complex, One or two or more selected from the group consisting of a metal β-iminone complex and a metal amino complex. Particularly suitable compounds are metal alkoxides, partial hydrolyzates, and organic acid salts. Among them, examples of the lead compound and the ruthenium compound include acetate (lead acetate: Pb(OAc) 2 , lanthanum acetate: La(OAc) 3 ), lead diisopropylate: Pb (OiPr) 2 , and lanthanum triisopropoxide. :La(OiPr) 3 and so on. As titanium compounds include titanium tetraethoxide: Ti (OEt) 4, titanium isopropoxide: Ti (OiPr) 4, tetra-n-butoxide titanium: Ti (OiBu) 4, tetra-iso-butoxide titanium: Ti (OiBu 4 , titanium tetra-t-butoxide: Ti(OtBu) 4 , dimethoxydiisopropyltitanium: alkoxide such as Ti(OMe) 2 (OiPr) 2 . As the zirconium compound, an alkoxide is preferred as the titanium compound. The metal alkoxide may be used as it is, and a hydrolyzate may be used in order to promote decomposition into the portion.
將這些原料以相當於所要的PZT系強介電質薄膜組成的比率溶解於適當的溶媒成為適於塗佈的濃度之同組成物的調製,以藉由如下的液合成流程為較佳。於反應容 器,加入Zr源、Ti源、安定化劑,在氮氣氛圍中迴流。其次在迴流後的化合物添加鉛源,同時添加溶劑,在氮氣氛圍中迴流,減壓蒸餾除去副產物之後,對此溶液進而添加丙二醇調節濃度,進而對此溶液添加正丁醇。 The preparation of these materials at a ratio corresponding to the desired PZT-based ferroelectric thin film is dissolved in a suitable solvent to prepare a composition suitable for coating at a concentration suitable for the liquid synthesis process as follows. Reaction capacity The Zr source, the Ti source, and the stabilizer were added and refluxed under a nitrogen atmosphere. Next, a lead source was added to the compound after the reflux, a solvent was added thereto, and the mixture was refluxed under a nitrogen atmosphere. After the by-product was distilled off under reduced pressure, the solution was further added with propylene glycol to adjust the concentration, and n-butanol was added to the solution.
此處使用的PZT系強介電質薄膜形成用組成物的溶媒,因應於使用的原料而適當決定,但一般而言,可以使用羰酸、醇(例如,多價醇之丙二醇(propylene glycol))、酯、酮類(例如丙酮、甲乙酮)、醚類(例如二甲基醚、二乙基醚)、環烷類(例如環己烷、環己醇)、芳香族系(例如苯、甲苯、二甲苯),其他四氫呋喃等,或者這些之2種以上的混合溶媒。 The solvent of the PZT-based ferroelectric thin film-forming composition used herein is appropriately determined depending on the raw materials to be used. However, in general, a carboxylic acid or an alcohol (for example, propylene glycol of a polyvalent alcohol) can be used. ), esters, ketones (such as acetone, methyl ethyl ketone), ethers (such as dimethyl ether, diethyl ether), naphthenes (such as cyclohexane, cyclohexanol), aromatic (such as benzene, toluene) , xylene), other tetrahydrofuran, or the like, or a mixed solvent of two or more of these.
作為前述之羧酸,具體而言,以使用n-酪酸、α-甲基酪酸、i-吉草酸、2-乙基酪酸、2,2-二甲基酪酸、3,3-二甲基酪酸、2,3-二甲基酪酸、3-甲基戊酸、4-甲基戊酸、2-乙基戊酸、3-乙基戊酸、2,2-二甲基戊酸、3,3-二甲基戊酸、2,3-二甲基戊酸、2-乙基己酸、3-乙基己酸為較佳。 As the carboxylic acid, specifically, n-butyric acid, α-methylbutyric acid, i-jilicic acid, 2-ethylbutyric acid, 2,2-dimethylbutyric acid, 3,3-dimethylbutyric acid are used. , 2,3-dimethylbutyric acid, 3-methylpentanoic acid, 4-methylpentanoic acid, 2-ethylpentanoic acid, 3-ethylpentanoic acid, 2,2-dimethylvaleric acid, 3, 3-dimethylvaleric acid, 2,3-dimethylvaleric acid, 2-ethylhexanoic acid, and 3-ethylhexanoic acid are preferred.
此外,作為前述之酯,以使用醋酸乙酯、醋酸丙酯、醋酸正丁酯、醋酸sec-丁酯、醋酸tert-丁酯、醋酸異丁酯、醋酸正戊酯、醋酸sec-戊酯、醋酸tert-戊酯、醋酸異戊酯為較佳;作為醇,以使用1-丙醇、2-丙醇、1-丁醇、2-丁醇、異丁醇、1-戊醇、2-戊醇、2-甲基-2-戊醇、2-甲氧基乙醇為適切。 Further, as the above ester, ethyl acetate, propyl acetate, n-butyl acetate, sec-butyl acetate, tert-butyl acetate, isobutyl acetate, n-amyl acetate, sec-amyl acetate, Tert-amyl acetate and isoamyl acetate are preferred; as the alcohol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, 1-pentanol, 2- Pentanol, 2-methyl-2-pentanol, and 2-methoxyethanol are suitable.
又,供形成PZT系強介電質薄膜之組成物的有機金屬化合物溶液中的有機金屬化合物的合計濃度,以金屬氧 化物換算量為0.1~23質量百分比(以下簡稱為質量%)程度為較佳。 Further, the total concentration of the organometallic compound in the organometallic compound solution for forming the composition of the PZT-based ferroelectric thin film is metal oxygen The amount of the compound to be converted is preferably from 0.1 to 23% by mass (hereinafter referred to as % by mass).
於此有機金屬化合物容液中,因應需要作為安定化劑,添加β-二酮類(例如乙醯基丙酮酸、五氟化丁醯基三甲基乙醯基甲烷、二三甲基乙烯基甲烷、三氟乙醯基丙酮酸、苯甲醯丙酮等)、β-酮類(例如,乙醯乙酸、丙酸基醋酸酯、苯甲酸乙酐等)、β-酮酯類(例如前述酮酸之甲基、丙基、丁基等低級烷酯類)、含氧酸類(例如,乳酸、甘醇酸、α-苯氧醋酸、水楊酸等),前述含氧酸之低級烷酯類,羥基酮類(例如二丙酮醇、乙醯乙醇等)二醇、三醇、高級羧酸、脂肪族胺類(例如二乙醇胺,三乙醇胺,單乙醇胺),多價胺等,(安定化劑分子數)/(金屬原子數)添加0.2~3程度亦可。 In the organometallic compound liquid, β-diketones (for example, acetyl thiopyruvate, butyl fluorenyltrimethyl ethane methacrylate, ditrimethyl vinyl methane, etc.) may be added as a stabilizer. Trifluoroethyl phthalic acid, benzamidine acetone, etc., β-ketones (for example, acetamidineacetic acid, propionic acid acetate, benzoic acid acetic anhydride, etc.), β-ketoesters (for example, the aforementioned keto acid) a lower alkyl ester such as a methyl group, a propyl group or a butyl group; an oxyacid (for example, lactic acid, glycolic acid, α-phenoxyacetic acid, salicylic acid, etc.), a lower alkyl ester of the above oxo acid, and a hydroxyl group. Ketones (eg, diacetone alcohol, acetamethanol, etc.) diols, triols, higher carboxylic acids, aliphatic amines (eg, diethanolamine, triethanolamine, monoethanolamine), polyvalent amines, etc. (number of stabilizers) ) / (the number of metal atoms) can also be added to the extent of 0.2 to 3.
此外,PZT系強介電質薄膜形成用組成物以含有β-二酮類及多價醇類亦可。其中,β-二酮類採用丙酮乙醯(acetyl acetone),多價醇類採用丙二醇(propylene glycol)為特佳。 Further, the PZT-based ferroelectric thin film-forming composition may contain a β-diketone or a polyvalent alcohol. Among them, β-diketones are acetylacetone, and polyvalent alcohols are preferably propylene glycol.
進而,前述調製的有機金屬化合物溶液,藉由過濾處理等,除去微粒為較佳。 Further, it is preferred that the prepared organometallic compound solution is subjected to a filtration treatment or the like to remove fine particles.
在此塗佈階段於製造PZT系強介電質薄膜,以CSD法,且以使用旋轉塗佈機之旋轉塗佈法為較佳,在組成物準備階段製作的溶液設置於旋轉塗佈機上在矽基板上依序 形成SiO2膜、TiO2膜及Pt膜的下部電極的Pt膜上滴下,以1500rpm~2000rpm進行60秒鐘的旋轉塗佈在Pt基板上形成塗佈膜。塗佈後,把被形成塗佈膜的基板配置於150℃的熱板上加熱3分鐘,除去低沸點溶媒或吸附的水分子,使該塗佈膜為凝膠狀的膜(以下稱為「凝膠膜」)。替代旋轉塗佈法,適當使用滴下法、LSMCD(Liquid Source Misted Chemical Deposition)法等其他之CSD法亦可。 In this coating stage, a PZT-based ferroelectric thin film is produced by a CSD method, and a spin coating method using a spin coater is preferred, and a solution prepared in a composition preparation stage is set on a spin coater. are sequentially formed on the SiO 2 film of silicon-based board, Pt lower electrode film, a TiO 2 film and a Pt film dropped to 1500rpm ~ 2000rpm spin coating for 60 seconds to form a coating film on the Pt substrate. After the application, the substrate on which the coating film was formed was placed on a hot plate at 150 ° C for 3 minutes to remove the low-boiling solvent or the adsorbed water molecules, and the coating film was a gel-like film (hereinafter referred to as " Gel film"). Instead of the spin coating method, other CSD methods such as a dropping method or a LSMCD (Liquid Source Misted Chemical Deposition) method may be suitably used.
在此暫燒結階段,除去凝膠膜中的溶媒或水分同時使有機金屬化合物熱分解或加水分解而轉化為複合氧化物。因此,在空氣中、氧化氛圍中,或者含水蒸氣氛圍中進行。在本說明書,<暫燒結階段>定義為作為複合氧化物之相在鈣鈦礦(perovskite)相在所要的PZT系強介電質薄膜中開始形成的溫度以下燒結凝膠膜之階段,另一方面,後述的<正式燒結階段>,定義為使在PZT系強介電質薄膜中形成鈣鈦礦(perovskite)相之階段。 In this temporary sintering stage, the solvent or moisture in the gel film is removed while the organometallic compound is thermally decomposed or hydrolyzed to be converted into a composite oxide. Therefore, it is carried out in the air, in an oxidizing atmosphere, or in a water vapor atmosphere. In the present specification, the <temporary sintering stage> is defined as a stage in which a phase of a composite oxide is sintered at a temperature below a temperature at which a perovskite phase begins to form in a desired PZT-based ferroelectric thin film, and another On the other hand, the <formal sintering stage> to be described later is defined as a stage in which a perovskite phase is formed in a PZT-based ferroelectric thin film.
進而詳言之,參照圖2,與相關於先前技術的一段暫燒結進行比較同時說明相關於本實施型態之二段暫燒結。 More specifically, referring to Fig. 2, a comparison with the prior art of a temporary sintering is performed while explaining the two-stage temporary sintering associated with the present embodiment.
圖2係橫軸以暫燒結的製程時間(秒)為參數,縱軸以暫燒結溫度(℃)為參數之暫燒結階段的溫度變化圖。在圖2,單點虛線係相關於本實施型態的二階段暫燒結的溫度變化圖,實線指先前技術之一段暫燒結的溫度變化 圖。 Fig. 2 is a graph showing the temperature change of the horizontal axis with the temporary sintering process time (second) as the parameter and the vertical axis with the temporary sintering temperature (°C) as the parameter. In Fig. 2, the single-dotted broken line is a temperature change diagram relating to the two-stage temporary sintering of the present embodiment, and the solid line refers to the temperature change of the temporary sintering of one of the prior art. Figure.
由圖2可知,在先前技術之一段暫燒結,為了提高生產性而使暫燒結溫度在直到保持溫度(在圖2為450℃)為止藉由RTA單調而且急劇上升的升溫速度17升溫,之後以一定的保持時間維持保持溫度18。另一方面,在本實施型態的暫燒結階段之二段暫燒結,設有第1保持階段14與第2保持階段16之二處保持溫度區域,由室溫等比較低的一定溫度起直到第1保持階段14為止由RTA以相當緩慢的升溫速度(第1升溫速度13)升溫,進而由第1保持基段14至第2保持階段16為止較佳者係以比第1升溫速度更快的第2升溫速度15升溫的方式進行暫燒結。在本實施型態,溫度的保持階段的數目而2處,但因應原料的組成或添加物的配合等,因應必要而設3處以上亦可。 As can be seen from Fig. 2, in the first stage of the prior art, in order to improve the productivity, the temporary sintering temperature is raised by the RTA monotonously and rapidly rising temperature rise rate 17 until the temperature is maintained (450 ° C in Fig. 2), and then A certain hold time is maintained at a temperature of 18. On the other hand, in the second-stage temporary sintering of the temporary sintering stage of the present embodiment, the temperature range of the first holding stage 14 and the second holding stage 16 is maintained, and the temperature is kept from a relatively low temperature such as room temperature until In the first holding phase 14, the RTA is heated at a relatively slow temperature increase rate (first temperature increase rate 13), and further preferably from the first holding base portion 14 to the second holding stage 16 is faster than the first temperature increase rate. The temporary sintering is performed in such a manner that the second temperature increase rate 15 is increased. In the present embodiment, the number of the temperature holding phases is two, but three or more may be provided as necessary depending on the composition of the raw materials or the blending of the additives.
而且,在前述之二段暫燒結使用紅外線。例如把產生紅外線的加熱器(未圖示)配置於基板10之下然後加熱凝膠膜的話,可以使殘留有機成分由凝膠膜除去(脫氣),而且可和緩地使凝膠膜熱分解、熱膨脹、熱收縮同時進行正式燒結。 Further, infrared rays are used for the temporary sintering in the second stage. For example, when a heater (not shown) that generates infrared rays is disposed under the substrate 10 and then heats the gel film, the residual organic component can be removed (degassed) from the gel film, and the gel film can be thermally decomposed smoothly. , thermal expansion, heat shrinking and simultaneous sintering.
依照圖2所示的二段暫燒結溫度變化圖之溫度,可以藉由把基板10配置於未圖示的紅外線加熱器之上,藉由被連接於紅外線加熱器的未圖示的溫度控制裝置來控制。根據相關的溫度控制,可以適當變更包含升溫速度、保持溫度、保持時間之溫度變化圖的條件。例如,如圖3所 示,顯示依照預先在溫度控制裝置設定程式之溫度變化圖(profile),針對暫燒結時的第1升溫速度可以選擇3種類之中的任一之二段暫燒結溫度變化圖。 According to the temperature of the two-stage temporary sintering temperature change diagram shown in FIG. 2, the substrate 10 can be placed on an infrared heater (not shown), and a temperature control device (not shown) connected to the infrared heater can be used. To control. According to the related temperature control, the conditions including the temperature change rate of the temperature increase rate, the holding temperature, and the holding time can be appropriately changed. For example, as shown in Figure 3. In addition, it is possible to select one of the three types of temporary sintering temperature change maps for the first temperature increase rate at the time of temporary sintering in accordance with the temperature profile of the temperature control device setting program.
進而詳言之,以下說明供進行該二段暫燒結之用的溫度變化圖之條件、理由。 Further, in detail, the conditions and reasons for the temperature change map for performing the two-stage temporary sintering will be described below.
第1保持階段的主要目的,是包含有PZT系強介電質薄膜組成物的溶液所含的高分子或溶媒等殘留有機物的分解、燃燒、乾燥。因此,第1保持階段的保持溫度太高的話,會因為殘留有機成分的燃燒等而局部產生非目標之氧化物而無法得到緻密均質的膜。因此,在第1保持階段採200℃~350℃之任一之保持溫度(例如275℃),保持1~5分鐘。其理由為第1保持階段的保持溫度未滿200℃的話不會充分促進前軀體的分解,而超過350℃的話,分解會進行得太過劇烈,會發生氣體造成空孔產生或者膜會收縮帶來應力導致龜裂產生的緣故。此外,第1保持階段的保持時間未滿1分鐘的話,前驅物質的分解會不夠充分,超過5分鐘的話會使生產性惡化。 The main purpose of the first holding step is decomposition, combustion, and drying of residual organic substances such as a polymer or a solvent contained in a solution containing a PZT-based ferroelectric thin film composition. Therefore, when the holding temperature in the first holding step is too high, a non-target oxide is locally generated due to combustion of residual organic components, and a dense and homogeneous film cannot be obtained. Therefore, in the first holding stage, the holding temperature (for example, 275 ° C) of any one of 200 ° C to 350 ° C is taken for 1 to 5 minutes. The reason is that if the holding temperature in the first holding stage is less than 200 ° C, the decomposition of the precursor is not sufficiently promoted, and if it exceeds 350 ° C, the decomposition proceeds too much, and gas generation may occur or the film may shrink. The stress causes the crack to occur. Further, when the holding time in the first holding stage is less than one minute, the decomposition of the precursor substance is insufficient, and if it exceeds 5 minutes, the productivity is deteriorated.
進而,在第1保持階段,較佳者為250℃~300℃之任一之保持溫度,較佳者為保持3~5分鐘。其理由是第1保持階段的保持溫度未滿250℃的話前軀體所含有的高分子等的分解會變得不充分會因氣體發生而誘發空孔的產生,而超過300℃的話,熱分解會劇烈進行,會有發生龜裂或空孔之虞。此外,第1保持階段的保持時間為1分鐘~5分鐘。其理由是第1保持階段的保持時間未滿1分鐘 的話,熱分解會不夠充分,超過5分鐘的話會使生產性惡化。 Further, in the first holding step, it is preferably a holding temperature of any one of 250 ° C to 300 ° C, preferably 3 to 5 minutes. The reason for this is that when the holding temperature in the first holding stage is less than 250 ° C, the decomposition of the polymer or the like contained in the precursor is insufficient, and the generation of voids is induced by the gas generation. When the temperature exceeds 300 ° C, the thermal decomposition occurs. If it is carried out violently, there will be cracks or holes. Further, the holding time in the first holding stage is 1 minute to 5 minutes. The reason is that the holding time of the first holding phase is less than 1 minute. If it is, the thermal decomposition will not be sufficient, and if it exceeds 5 minutes, the productivity will deteriorate.
此外,0℃~150℃的溫度範圍內的溫度(或者室溫)起以升溫速度1℃/秒~50℃/秒(第1升溫速度)升溫至第1保持階段的保持溫度為止。其理由是第1升溫速度未滿1℃/秒的話生產性很差,超過50℃/秒的話會因為過衝(over-shoot)而有使膜的一部分結晶化之虞。進而,第1升溫速度較佳者為2.5℃/秒~10℃/秒。其理由為第1升溫速度未滿2.5℃的話生產性很差,超過10℃/秒的話,前軀體的分解會進行得太過劇烈的緣故。 Further, the temperature (or room temperature) in the temperature range of 0 ° C to 150 ° C is raised to a holding temperature in the first holding stage at a temperature increase rate of 1 ° C / sec to 50 ° C / sec (first temperature increase rate). The reason is that when the first temperature increase rate is less than 1 ° C / sec, productivity is poor, and when it exceeds 50 ° C / sec, a part of the film is crystallized due to over-shoot. Further, the first temperature increase rate is preferably from 2.5 ° C / sec to 10 ° C / sec. The reason for this is that when the first temperature increase rate is less than 2.5 ° C, the productivity is poor, and if it exceeds 10 ° C / sec, the decomposition of the precursor is too intense.
其次,第2保持階段的主要目的為除去在第1保持時間無法除去的微量金屬烷氧化物(alkoxide)所帶來的烷氧基或者作為安定化劑而添加的有機配位子,另外還有非晶質膜的緻密化。因此,在第2保持階段採350℃~500℃之任一之保持溫度(例如450℃),保持5~10分鐘。其理由為第2階段的保持溫度未滿350℃熱分解不充分的話,膜中容易生成不要的氧化物的緣故,而超過500℃的話膜的一部分會變成鈣鈦礦(perovskite)相而難以得到類磊晶的膜。 Next, the main purpose of the second holding stage is to remove an alkoxy group derived from a trace amount of alkoxide which cannot be removed at the first holding time or an organic ligand which is added as a stabilizer, and Densification of an amorphous film. Therefore, in the second holding stage, the holding temperature (for example, 450 ° C) of any of 350 ° C to 500 ° C is maintained for 5 to 10 minutes. When the thermal decomposition of the second stage is less than 350 ° C, the film is likely to form an unnecessary oxide, and when it exceeds 500 ° C, a part of the film becomes a perovskite phase, which is difficult to obtain. Epitaxial film.
此外,由第1保持階段到第2保持階段為止,儘可能進行PZT系強介電質薄膜之膜的緻密化。因此,以升溫速度1℃/秒~100℃/秒(第2升溫速度)升溫至第2保持階段的保持溫度。其理由為第2升溫速度未滿1℃/秒的話生產性很差,而超過100℃/秒的話會因為急遽的熱分解而 使目的以外的氧化物在膜中產生的緣故。進而,第2升溫速度較佳者為2.5℃/秒~50℃/秒。其理由為第2升溫速度未滿2.5℃的話生產性很差,超過50℃/秒的話,前軀體的分解會急遽進行而使緻密化不進行的緣故。 Further, the film of the PZT-based ferroelectric thin film is densified as much as possible from the first holding stage to the second holding stage. Therefore, the temperature is raised to the holding temperature in the second holding stage at a temperature increase rate of 1 ° C / sec to 100 ° C / sec (second temperature increase rate). The reason is that if the second temperature increase rate is less than 1 ° C / sec, the productivity is poor, and if it exceeds 100 ° C / sec, it will be due to rapid thermal decomposition. The reason why an oxide other than the target is generated in the film. Further, the second temperature increase rate is preferably from 2.5 ° C / sec to 50 ° C / sec. When the second temperature increase rate is less than 2.5 ° C, the productivity is poor. When the temperature exceeds 50 ° C / sec, the decomposition of the precursor is rapidly performed and the densification is not performed.
此外,第2階段的保持時間,為了要充分促進PZT系強介電質薄膜的非晶化而採3分鐘~20分鐘。其理由是第2保持階段的保持時間未滿3分鐘的話,前軀體的熱分解會不充分,超過3分鐘的話會使反應充分進行的緣故。進而,第2保持階段的保持時間,較佳為3分鐘~10分鐘。其理由為第2保持階段的保持時間未滿3分鐘的話,前軀體的熱分解會不充分,超過10分鐘的話,熱分解幾乎結束,對於膜的配向性等不會有較大的影響的緣故。 Further, the holding time in the second stage is carried out for 3 minutes to 20 minutes in order to sufficiently promote the amorphization of the PZT-based ferroelectric thin film. The reason is that if the holding time in the second holding stage is less than 3 minutes, the thermal decomposition of the precursor is insufficient, and if it exceeds 3 minutes, the reaction proceeds sufficiently. Further, the holding time in the second holding stage is preferably from 3 minutes to 10 minutes. When the holding time of the second holding stage is less than 3 minutes, the thermal decomposition of the precursor is insufficient. When the holding time exceeds 10 minutes, the thermal decomposition is almost completed, and the film has no significant influence on the alignment property and the like. .
此正式燒結階段,係以使在暫燒結階段所得到的PZT系強介電質薄膜在結晶化溫度以上的溫度正式燒結使結晶化之階段,經此階段可得到具備鈣鈦礦(perovskite)相的PZT系強介電質薄膜。此結晶化步驟之燒結氛圍為O2、N2、Ar、N2O或H2等,或者這些的混合氣體為適切。 In the formal sintering stage, the PZT-based ferroelectric thin film obtained in the temporary sintering stage is sintered at a temperature higher than the crystallization temperature to form a crystallization stage, and a perovskite phase can be obtained at this stage. PZT is a ferroelectric thin film. The sintering atmosphere of this crystallization step is O 2 , N 2 , Ar, N 2 O or H 2 or the like, or a mixed gas of these is suitable.
該正式燒結在450℃~800℃進行1分鐘~60分鐘,為了要提高生產效率也可以採用RTA處理。其理由是正式燒結溫度未滿450℃的話無法得到鈣鈦礦(perovskite) 相,超過800℃時膜特性會惡化。此外,未滿1分鐘的話正式燒結不夠充分,超過60分鐘的話會使生產性惡化。較佳者為正式燒結溫度、正式燒結時間較佳者為600℃~700℃進行1分鐘~5分鐘。其理由是正式燒結溫度未滿600℃的話若非特殊的溶液或正式燒結氛圍就無法得到結晶性高的膜,超過700℃的話膜特性會惡化。此外,不滿1分鐘的話,正式燒結不夠充分,超過5分鐘的話,除了特殊的溶液或正式燒結氛圍以外無法更加進行結晶化。以RTA處理進行正式燒結的場合,使其升溫速度為2.5℃/秒~150℃/秒。此場合,較佳者為其升溫速度為10℃/秒~100℃/秒。升溫速度未滿10℃/秒的話生產性很差,超過100℃/秒的話相關於正式燒結的裝置之控制會很困難。 The main sintering is carried out at 450 ° C to 800 ° C for 1 minute to 60 minutes, and in order to improve production efficiency, RTA treatment can also be employed. The reason is that perovskite cannot be obtained if the formal sintering temperature is less than 450 °C. The film properties deteriorate when the temperature exceeds 800 °C. In addition, if it is less than one minute, the actual sintering is insufficient, and if it exceeds 60 minutes, the productivity will deteriorate. Preferably, the main sintering temperature and the main sintering time are preferably from 600 ° C to 700 ° C for 1 minute to 5 minutes. The reason is that if the main sintering temperature is less than 600 ° C, a film having high crystallinity cannot be obtained unless it is a special solution or a main sintering atmosphere, and when it exceeds 700 ° C, the film properties are deteriorated. In addition, if it is less than 1 minute, the actual sintering is insufficient, and if it exceeds 5 minutes, it cannot crystallize further than a special solution or a formal sintering atmosphere. When the main sintering is performed by RTA treatment, the temperature increase rate is 2.5 ° C / sec to 150 ° C / sec. In this case, it is preferred that the temperature increase rate is from 10 ° C / sec to 100 ° C / sec. When the temperature rise rate is less than 10 ° C / sec, the productivity is poor, and if it exceeds 100 ° C / sec, it is difficult to control the apparatus related to the main sintering.
如以上所述藉由本實施型態所製造的PZT系強介電質薄膜,藉由適宜的加工,可以使用於薄膜電容器、電容器、IPD、DRAM記憶體用電容器、層積電容器、電晶體之閘極絕緣體、非易失性記憶體,焦電型紅外線檢測元件、壓電元件、光電元件、致動器、共振子、超音波馬達、或LC雜訊過濾元件之複合電子零件。 The PZT-based ferroelectric thin film manufactured by the present embodiment as described above can be used for film capacitors, capacitors, capacitors for IPD, DRAM memory, laminated capacitors, and gates of transistors by suitable processing. A composite electronic component of a pole insulator, a nonvolatile memory, a pyroelectric infrared detecting element, a piezoelectric element, a photovoltaic element, an actuator, a resonator, an ultrasonic motor, or an LC noise filter element.
其次參照相關於先前技術之比較例同時參照圖3、圖4、圖5、圖6以及表1、2同時詳細說明相關於本發明的實施例。 Next, an embodiment related to the present invention will be described in detail with reference to a comparative example related to the prior art while referring to FIG. 3, FIG. 4, FIG. 5, FIG. 6, and Tables 1, 2.
實施例,係由組成物準備階段、塗佈階段、使用紅外 線之二階段暫燒結之暫燒結階段及正式燒結階段,而得到16種PZT系強介電質薄膜。另一方面,比較例,係由組成物準備階段、塗佈階段、不設從前的保持階段之暫燒結階段及正式燒結階段,而得到5種PZT系強介電質薄膜。於表1、表2整理了各實施例之暫燒結階段的第1保持溫度、第1升溫速度及第2升溫溫度、第2升溫速度之條件。於此表1、表2,對各條件,整理了暫燒結後、正式燒結後的膜厚及折射率之值,針對測定方法、評估方法、評估結果於稍後敘述。 The embodiment is composed of a composition preparation stage, a coating stage, and an infrared Sixteen PZT-based ferroelectric thin films were obtained in the temporary sintering stage and the formal sintering stage of the second-stage temporary sintering. On the other hand, in the comparative example, five types of PZT-based ferroelectric thin films were obtained from the composition preparation stage, the coating stage, and the temporary sintering stage and the main sintering stage in which the previous holding stage was not provided. The conditions of the first holding temperature, the first temperature increase rate, the second temperature increase temperature, and the second temperature increase rate in the temporary sintering stage of each of the examples are summarized in Tables 1 and 2. In Tables 1 and 2, the values of the film thickness and the refractive index after the temporary sintering and the main sintering are prepared for each condition, and the measurement method, the evaluation method, and the evaluation results will be described later.
組成物準備階段及塗佈階段,是全部實施例及比較例共通包含的階段,以如下的方式進行。 The composition preparation stage and the coating stage are stages which are common to all the examples and the comparative examples, and are carried out as follows.
首先,在組成物準備階段,以Pb:Zr:Ti組成比成為115:52:48(氧化物換算為25wt%)的方式把24.24g之Pb(CH3COO)3).3H2O、13.44g之Zr(Oi-Pr)4、7.64g之Ti(Oi-Pr)4溶解於乙醇與丙二醇(propylene glycol)之混合溶液,而且作為安定化劑添加丙酮乙醯者作為PZT系強介電質組成物之原料溶液。進而,對此原料溶液以使莫耳比成為PZT:聚乙烯吡咯啶酮=1:0.5的方式添加聚乙烯吡咯啶酮,在常溫攪拌24小時。接著,對原料溶液添加N-甲基甲醯胺使成為7wt%的濃度,攪拌2小時後,24小時在室溫下使安定化。 First, in the composition preparation stage, 24.24 g of Pb(CH 3 COO) 3 ) was obtained in such a manner that the Pb:Zr:Ti composition ratio was 115:52:48 (25 wt% in terms of oxide). 3H 2 O, 13.44g of Zr(Oi-Pr) 4 , 7.64g of Ti(Oi-Pr) 4 dissolved in a mixed solution of ethanol and propylene glycol, and as a stabilizer, acetone is added as PZT A raw material solution of a strong dielectric composition. Further, this raw material solution was added with polyvinylpyrrolidone so that the molar ratio became PZT: polyvinylpyrrolidone = 1:0.5, and the mixture was stirred at normal temperature for 24 hours. Next, N-methylformamide was added to the raw material solution to have a concentration of 7 wt%, and after stirring for 2 hours, it was stabilized at room temperature for 24 hours.
接著,在塗佈階段,把組成物準備階段得到的溶液滴下到設置於旋轉塗佈器上的Si/SiO2/TiO2/Pt基板,以2000rmp進行60秒旋轉塗佈形成塗佈膜。此外,於暫燒 結階段前把塗佈膜在150℃的熱板上加熱3分鐘,得到除去低沸點溶媒或吸附的水分子之凝膠膜。 Next, in the coating stage, the solution obtained in the composition preparation stage was dropped onto a Si/SiO 2 /TiO 2 /Pt substrate provided on a spin coater, and spin-coated at 2000 rpm for 60 seconds to form a coating film. Further, the coating film was heated on a hot plate at 150 ° C for 3 minutes before the temporary sintering stage to obtain a gel film which removed the low-boiling solvent or the adsorbed water molecules.
在實施例1,把塗佈階段得到的凝膠膜,於根據二段暫燒結的暫燒結階段藉由紅外線來暫燒結。具體的暫燒結條件,為以升溫速度1℃/秒由25℃升溫至275℃,保持3分鐘後,以升溫速度2.5℃/秒升溫至450℃保持5分鐘。接著於正式燒結階段,把在暫燒結階段所得到的非晶質膜以升溫速度5℃/秒,在700℃保持時間5分鐘進行正式燒結而得PZT系強介電質薄膜。 In Example 1, the gel film obtained in the coating stage was temporarily sintered by infrared rays in the temporary sintering stage according to the two-stage temporary sintering. The specific temporary sintering conditions were such that the temperature was raised from 25 ° C to 275 ° C at a temperature increase rate of 1 ° C / sec, and after maintaining for 3 minutes, the temperature was raised to 450 ° C at a temperature increase rate of 2.5 ° C / sec for 5 minutes. Then, in the main sintering stage, the amorphous film obtained in the temporary sintering stage was subjected to main sintering at a temperature increase rate of 5 ° C / sec and held at 700 ° C for 5 minutes to obtain a PZT-based ferroelectric thin film.
在實施例2,把塗佈階段得到的凝膠膜,於根據二段暫燒結的暫燒結階段藉由紅外線來暫燒結。具體的暫燒結條件,為以升溫速度1℃/秒由25℃升溫至275℃,保持3分鐘後,以升溫速度10℃/秒升溫至450℃保持5分鐘。接著於正式燒結階段,把在暫燒結階段所得到的非晶質膜以升溫速度5℃/秒,在700℃保持時間5分鐘進行正式燒結而得PZT系強介電質薄膜。 In Example 2, the gel film obtained in the coating stage was temporarily sintered by infrared rays in the temporary sintering stage according to the two-stage temporary sintering. The specific temporary sintering conditions were such that the temperature was raised from 25 ° C to 275 ° C at a temperature increase rate of 1 ° C / sec, and after maintaining for 3 minutes, the temperature was raised to 450 ° C at a temperature increase rate of 10 ° C / sec for 5 minutes. Then, in the main sintering stage, the amorphous film obtained in the temporary sintering stage was subjected to main sintering at a temperature increase rate of 5 ° C / sec and held at 700 ° C for 5 minutes to obtain a PZT-based ferroelectric thin film.
在實施例3,把塗佈階段得到的凝膠膜,於根據二段暫燒結的暫燒結階段藉由紅外線來暫燒結。具體的暫燒結 條件,為以升溫速度1℃/秒由25℃升溫至275℃,保持3分鐘後,以升溫速度25℃/秒升溫至450℃保持5分鐘。接著於正式燒結階段,把在暫燒結階段所得到的非晶質膜以升溫速度5℃/秒,在700℃保持時間5分鐘進行正式燒結而得PZT系強介電質薄膜。 In Example 3, the gel film obtained in the coating stage was temporarily sintered by infrared rays in the temporary sintering stage according to the two-stage temporary sintering. Specific temporary sintering The temperature was raised from 25 ° C to 275 ° C at a temperature increase rate of 1 ° C / sec, and after maintaining for 3 minutes, the temperature was raised to 450 ° C at a temperature increase rate of 25 ° C / sec for 5 minutes. Then, in the main sintering stage, the amorphous film obtained in the temporary sintering stage was subjected to main sintering at a temperature increase rate of 5 ° C / sec and held at 700 ° C for 5 minutes to obtain a PZT-based ferroelectric thin film.
在實施例4,把塗佈階段得到的凝膠膜,於根據二段暫燒結的暫燒結階段藉由紅外線來暫燒結。具體的暫燒結條件,為以升溫速度1℃/秒由25℃升溫至275℃,保持3分鐘後,以升溫速度50℃/秒升溫至450℃保持5分鐘。接著於正式燒結階段,把在暫燒結階段所得到的非晶質膜以升溫速度5℃/秒,在700℃保持時間5分鐘進行正式燒結而得PZT系強介電質薄膜。 In Example 4, the gel film obtained in the coating stage was temporarily sintered by infrared rays in the temporary sintering stage according to the two-stage temporary sintering. The specific temporary sintering conditions were such that the temperature was raised from 25 ° C to 275 ° C at a temperature increase rate of 1 ° C / sec, and after maintaining for 3 minutes, the temperature was raised to 450 ° C at a temperature increase rate of 50 ° C / sec for 5 minutes. Then, in the main sintering stage, the amorphous film obtained in the temporary sintering stage was subjected to main sintering at a temperature increase rate of 5 ° C / sec and held at 700 ° C for 5 minutes to obtain a PZT-based ferroelectric thin film.
在實施例5,把塗佈階段得到的凝膠膜,於根據二段暫燒結的暫燒結階段藉由紅外線來暫燒結。具體的暫燒結條件,為以升溫速度2.5℃/秒由25℃升溫至275℃,保持3分鐘後,以升溫速度2.5℃/秒升溫至450℃保持5分鐘。接著於正式燒結階段,把在暫燒結階段所得到的非晶質膜以升溫速度5℃/秒,在700℃保持時間5分鐘進行正式燒結而得PZT系強介電質薄膜。 In Example 5, the gel film obtained in the coating stage was temporarily sintered by infrared rays in the temporary sintering stage according to the two-stage temporary sintering. The specific temporary sintering conditions were such that the temperature was raised from 25 ° C to 275 ° C at a temperature increase rate of 2.5 ° C / sec, and after maintaining for 3 minutes, the temperature was raised to 450 ° C at a temperature increase rate of 2.5 ° C / sec for 5 minutes. Then, in the main sintering stage, the amorphous film obtained in the temporary sintering stage was subjected to main sintering at a temperature increase rate of 5 ° C / sec and held at 700 ° C for 5 minutes to obtain a PZT-based ferroelectric thin film.
在實施例6,把塗佈階段得到的凝膠膜,於根據二段暫燒結的暫燒結階段藉由紅外線來暫燒結。具體的暫燒結條件,為以升溫速度2.5℃/秒由25℃升溫至275℃,保持3分鐘後,以升溫速度10℃/秒升溫至450℃保持5分鐘。接著於正式燒結階段,把在暫燒結階段所得到的非晶質膜以升溫速度5℃/秒,在700℃保持時間5分鐘進行正式燒結而得PZT系強介電質薄膜。 In Example 6, the gel film obtained in the coating stage was temporarily sintered by infrared rays in the temporary sintering stage according to the two-stage temporary sintering. The specific temporary sintering conditions were such that the temperature was raised from 25 ° C to 275 ° C at a temperature increase rate of 2.5 ° C / sec, and after maintaining for 3 minutes, the temperature was raised to 450 ° C at a temperature increase rate of 10 ° C / sec for 5 minutes. Then, in the main sintering stage, the amorphous film obtained in the temporary sintering stage was subjected to main sintering at a temperature increase rate of 5 ° C / sec and held at 700 ° C for 5 minutes to obtain a PZT-based ferroelectric thin film.
在實施例7,把塗佈階段得到的凝膠膜,於根據二段暫燒結的暫燒結階段藉由紅外線來暫燒結。具體的暫燒結條件,為以升溫速度2.5℃/秒由25℃升溫至275℃,保持3分鐘後,以升溫速度10℃/秒升溫至450℃保持5分鐘。接著於正式燒結階段,把在暫燒結階段所得到的非晶質膜以升溫速度5℃/秒,在700℃保持時間5分鐘進行正式燒結而得PZT系強介電質薄膜。 In Example 7, the gel film obtained in the coating stage was temporarily sintered by infrared rays in the temporary sintering stage according to the two-stage temporary sintering. The specific temporary sintering conditions were such that the temperature was raised from 25 ° C to 275 ° C at a temperature increase rate of 2.5 ° C / sec, and after maintaining for 3 minutes, the temperature was raised to 450 ° C at a temperature increase rate of 10 ° C / sec for 5 minutes. Then, in the main sintering stage, the amorphous film obtained in the temporary sintering stage was subjected to main sintering at a temperature increase rate of 5 ° C / sec and held at 700 ° C for 5 minutes to obtain a PZT-based ferroelectric thin film.
在實施例8,把塗佈階段得到的凝膠膜,於根據二段暫燒結的暫燒結階段藉由紅外線來暫燒結。具體的暫燒結條件,為以升溫速度2.5℃/秒由25℃升溫至275℃,保持3分鐘後,以升溫速度50℃/秒升溫至450℃保持5分鐘。接著於正式燒結階段,把在暫燒結階段所得到的非晶質膜 以升溫速度5℃/秒,在700℃保持時間5分鐘進行正式燒結而得PZT系強介電質薄膜。 In Example 8, the gel film obtained in the coating stage was temporarily sintered by infrared rays in the temporary sintering stage according to the two-stage temporary sintering. The specific temporary sintering conditions were such that the temperature was raised from 25 ° C to 275 ° C at a temperature increase rate of 2.5 ° C / sec, and after maintaining for 3 minutes, the temperature was raised to 450 ° C at a temperature increase rate of 50 ° C / sec for 5 minutes. Then in the formal sintering stage, the amorphous film obtained in the temporary sintering stage is obtained. The PZT-based ferroelectric thin film was obtained by performing main sintering at a heating rate of 5 ° C / sec and holding at 700 ° C for 5 minutes.
在實施例9,把塗佈階段得到的凝膠膜,於根據二段暫燒結的暫燒結階段藉由紅外線來暫燒結。具體的暫燒結條件,為以升溫速度10℃/秒由25℃升溫至275℃,保持3分鐘後,以升溫速度2.5℃/秒升溫至450℃保持5分鐘。接著於正式燒結階段,把在暫燒結階段所得到的非晶質膜以升溫速度5℃/秒,在700℃保持時間5分鐘進行正式燒結而得PZT系強介電質薄膜。 In Example 9, the gel film obtained in the coating stage was temporarily sintered by infrared rays in the temporary sintering stage according to the two-stage temporary sintering. The specific temporary sintering conditions were such that the temperature was raised from 25 ° C to 275 ° C at a temperature increase rate of 10 ° C / sec, and after maintaining for 3 minutes, the temperature was raised to 450 ° C at a temperature increase rate of 2.5 ° C / sec for 5 minutes. Then, in the main sintering stage, the amorphous film obtained in the temporary sintering stage was subjected to main sintering at a temperature increase rate of 5 ° C / sec and held at 700 ° C for 5 minutes to obtain a PZT-based ferroelectric thin film.
在實施例10,把塗佈階段得到的凝膠膜,於根據二段暫燒結的暫燒結階段藉由紅外線來暫燒結。具體的暫燒結條件,為以升溫速度10℃/秒由25℃升溫至275℃,保持3分鐘後,以升溫速度10℃/秒升溫至450℃保持5分鐘。接著於正式燒結階段,把在暫燒結階段所得到的非晶質膜以升溫速度5℃/秒,在700℃保持時間5分鐘進行正式燒結而得PZT系強介電質薄膜。 In Example 10, the gel film obtained in the coating stage was temporarily sintered by infrared rays in the temporary sintering stage according to the second-stage temporary sintering. The specific temporary sintering conditions were such that the temperature was raised from 25 ° C to 275 ° C at a temperature increase rate of 10 ° C / sec, and after maintaining for 3 minutes, the temperature was raised to 450 ° C at a temperature increase rate of 10 ° C / sec for 5 minutes. Then, in the main sintering stage, the amorphous film obtained in the temporary sintering stage was subjected to main sintering at a temperature increase rate of 5 ° C / sec and held at 700 ° C for 5 minutes to obtain a PZT-based ferroelectric thin film.
在實施例11,把塗佈階段得到的凝膠膜,於根據二段暫燒結的暫燒結階段藉由紅外線來暫燒結。具體的暫燒 結條件,為以升溫速度10℃/秒由25℃升溫至275℃,保持3分鐘後,以升溫速度25℃/秒升溫至450℃保持5分鐘。接著於正式燒結階段,把在暫燒結階段所得到的非晶質膜以升溫速度5℃/秒,在700℃保持時間5分鐘進行正式燒結而得PZT系強介電質薄膜。 In Example 11, the gel film obtained in the coating stage was temporarily sintered by infrared rays in the temporary sintering stage according to the two-stage temporary sintering. Specific temporary burning The conditions were as follows: the temperature was raised from 25 ° C to 275 ° C at a temperature increase rate of 10 ° C / sec, and after maintaining for 3 minutes, the temperature was raised to 450 ° C at a temperature increase rate of 25 ° C / sec for 5 minutes. Then, in the main sintering stage, the amorphous film obtained in the temporary sintering stage was subjected to main sintering at a temperature increase rate of 5 ° C / sec and held at 700 ° C for 5 minutes to obtain a PZT-based ferroelectric thin film.
在實施例12,把塗佈階段得到的凝膠膜,於根據二段暫燒結的暫燒結階段藉由紅外線來暫燒結。具體的暫燒結條件,為以升溫速度10℃/秒由25℃升溫至275℃,保持3分鐘後,以升溫速度50℃/秒升溫至450℃保持5分鐘。接著於正式燒結階段,把在暫燒結階段所得到的非晶質膜以升溫速度5℃/秒,在700℃保持時間5分鐘進行正式燒結而得PZT系強介電質薄膜。 In Example 12, the gel film obtained in the coating stage was temporarily sintered by infrared rays in the temporary sintering stage according to the two-stage temporary sintering. The specific temporary sintering conditions were such that the temperature was raised from 25 ° C to 275 ° C at a temperature increase rate of 10 ° C / sec, and after maintaining for 3 minutes, the temperature was raised to 450 ° C at a temperature increase rate of 50 ° C / sec for 5 minutes. Then, in the main sintering stage, the amorphous film obtained in the temporary sintering stage was subjected to main sintering at a temperature increase rate of 5 ° C / sec and held at 700 ° C for 5 minutes to obtain a PZT-based ferroelectric thin film.
在實施例13,把塗佈階段得到的凝膠膜,於根據二段暫燒結的暫燒結階段藉由紅外線來暫燒結。具體的暫燒結條件,為以升溫速度2.5℃/秒由25℃升溫至275℃,保持3分鐘後,以升溫速度10℃/秒升溫至450℃保持5分鐘。接著於正式燒結階段,把在暫燒結階段所得到的非晶質膜以升溫速度5℃/秒,在700℃保持時間5分鐘進行正式燒結而得PZT系強介電質薄膜。 In Example 13, the gel film obtained in the coating stage was temporarily sintered by infrared rays in the temporary sintering stage according to the two-stage temporary sintering. The specific temporary sintering conditions were such that the temperature was raised from 25 ° C to 275 ° C at a temperature increase rate of 2.5 ° C / sec, and after maintaining for 3 minutes, the temperature was raised to 450 ° C at a temperature increase rate of 10 ° C / sec for 5 minutes. Then, in the main sintering stage, the amorphous film obtained in the temporary sintering stage was subjected to main sintering at a temperature increase rate of 5 ° C / sec and held at 700 ° C for 5 minutes to obtain a PZT-based ferroelectric thin film.
在實施例14,把塗佈階段得到的凝膠膜,於根據二段暫燒結的暫燒結階段藉由紅外線來暫燒結。具體的暫燒結條件,為以升溫速度2.5℃/秒由25℃升溫至300℃,保持3分鐘後,以升溫速度10℃/秒升溫至450℃保持5分鐘。接著於正式燒結階段,把在暫燒結階段所得到的非晶質膜以升溫速度5℃/秒,在700℃保持時間5分鐘進行正式燒結而得PZT系強介電質薄膜。 In Example 14, the gel film obtained in the coating stage was temporarily sintered by infrared rays in the temporary sintering stage according to the two-stage temporary sintering. The specific temporary sintering conditions were such that the temperature was raised from 25 ° C to 300 ° C at a temperature increase rate of 2.5 ° C / sec, and after maintaining for 3 minutes, the temperature was raised to 450 ° C at a temperature increase rate of 10 ° C / sec for 5 minutes. Then, in the main sintering stage, the amorphous film obtained in the temporary sintering stage was subjected to main sintering at a temperature increase rate of 5 ° C / sec and held at 700 ° C for 5 minutes to obtain a PZT-based ferroelectric thin film.
在實施例15,把塗佈階段得到的凝膠膜,於根據二段暫燒結的暫燒結階段藉由紅外線來暫燒結。具體的暫燒結條件,為以升溫速度2.5℃/秒由25℃升溫至275℃,保持3分鐘後,以升溫速度10℃/秒升溫至425℃保持5分鐘。接著於正式燒結階段,把在暫燒結階段所得到的非晶質膜以升溫速度5℃/秒,在700℃保持時間5分鐘進行正式燒結而得PZT系強介電質薄膜。 In Example 15, the gel film obtained in the coating stage was temporarily sintered by infrared rays in the temporary sintering stage according to the two-stage temporary sintering. The specific temporary sintering conditions were such that the temperature was raised from 25 ° C to 275 ° C at a temperature increase rate of 2.5 ° C / sec, and after maintaining for 3 minutes, the temperature was raised to 425 ° C at a temperature increase rate of 10 ° C / sec for 5 minutes. Then, in the main sintering stage, the amorphous film obtained in the temporary sintering stage was subjected to main sintering at a temperature increase rate of 5 ° C / sec and held at 700 ° C for 5 minutes to obtain a PZT-based ferroelectric thin film.
在實施例16,把塗佈階段得到的凝膠膜,於根據二段暫燒結的暫燒結階段藉由紅外線來暫燒結。具體的暫燒結條件,為以升溫速度2.5℃/秒由25℃升溫至275℃,保持3分鐘後,以升溫速度10℃/秒升溫至475℃保持5分鐘。接著於正式燒結階段,把在暫燒結階段所得到的非晶 質膜以升溫速度5℃/秒,在700℃保持時間5分鐘進行正式燒結而得PZT系強介電質薄膜。 In Example 16, the gel film obtained in the coating stage was temporarily sintered by infrared rays in the temporary sintering stage according to the two-stage temporary sintering. The specific temporary sintering conditions were such that the temperature was raised from 25 ° C to 275 ° C at a temperature increase rate of 2.5 ° C / sec, and after maintaining for 3 minutes, the temperature was raised to 475 ° C at a temperature increase rate of 10 ° C / sec for 5 minutes. Then in the formal sintering stage, the amorphous obtained in the temporary sintering stage The plasma film was subjected to main sintering at a temperature increase rate of 5 ° C / sec and held at 700 ° C for 5 minutes to obtain a PZT-based ferroelectric thin film.
在比較例1,把在塗佈階段得到的凝膠膜,在根據從前的一段暫燒結之暫燒結階段以升溫速度10℃/秒,升溫至400℃,在此溫度保持8分鐘進行暫燒結,接著於正式燒結階段,把暫燒結階段得到的膜以升溫速度10℃/秒,700℃,5分鐘之條件正式燒結而得到PZT系強介電質薄膜。 In Comparative Example 1, the gel film obtained in the coating stage was heated to 400 ° C at a temperature increase rate of 10 ° C / sec according to the temporary sintering stage of the prior period, and was temporarily sintered at this temperature for 8 minutes. Then, in the main sintering stage, the film obtained in the temporary sintering stage was sintered at a temperature rising rate of 10 ° C / sec and 700 ° C for 5 minutes to obtain a PZT-based ferroelectric thin film.
在比較例2,把在塗佈階段得到的凝膠膜,在根據從前之一段暫燒結的暫燒結階段,以升溫速度10℃/秒,升溫至450℃,在此溫度保持8分鐘進行暫燒結,接著於正式燒結階段,把暫燒結階段得到的膜以升溫速度10℃/秒,700℃,5分鐘之條件正式燒結而得到PZT系強介電質薄膜。 In Comparative Example 2, the gel film obtained in the coating stage was heated to 450 ° C at a temperature increase rate of 10 ° C / sec in a temporary sintering stage in which the first stage was temporarily sintered, and held at this temperature for 8 minutes for temporary sintering. Then, in the main sintering stage, the film obtained in the temporary sintering stage was sintered at a temperature rising rate of 10 ° C / sec, 700 ° C for 5 minutes to obtain a PZT-based ferroelectric thin film.
在比較例3,把在塗佈階段得到的凝膠膜,在根據從前之一段暫燒結的暫燒結階段,以升溫速度10℃/秒,升溫至475℃,在此溫度保持8分鐘進行暫燒結,接著於正式燒結階段,把暫燒結階段得到的膜以升溫速度10℃/ 秒,700℃,5分鐘之條件正式燒結而得到PZT系強介電質薄膜。 In Comparative Example 3, the gel film obtained in the coating stage was heated to 475 ° C at a temperature increase rate of 10 ° C / sec in the temporary sintering stage of the temporary sintering, and the temperature was maintained for 8 minutes for temporary sintering. Then, in the formal sintering stage, the film obtained in the temporary sintering stage is heated at a rate of 10 ° C / The PZT-based ferroelectric thin film was obtained by firing at a temperature of 700 ° C for 5 minutes.
在比較例4,把在塗佈階段得到的凝膠膜,在根據從前之一段暫燒結的暫燒結階段,以升溫速度10℃/秒,升溫至500℃,在此溫度保持8分鐘進行暫燒結,接著於正式燒結階段,把暫燒結階段得到的膜以升溫速度10℃/秒,700℃,5分鐘之條件正式燒結而得到PZT系強介電質薄膜。 In Comparative Example 4, the gel film obtained in the coating stage was heated to 500 ° C at a temperature increase rate of 10 ° C / sec in the temporary sintering stage of the temporary sintering, and the temperature was maintained for 8 minutes for temporary sintering. Then, in the main sintering stage, the film obtained in the temporary sintering stage was sintered at a temperature rising rate of 10 ° C / sec, 700 ° C for 5 minutes to obtain a PZT-based ferroelectric thin film.
在比較例5,把在塗佈階段得到的凝膠膜,在根據從前之一段暫燒結的暫燒結階段,以升溫速度2.5℃/秒,升溫至450℃,在此溫度保持8分鐘進行暫燒結,接著於正式燒結階段,把暫燒結階段得到的膜以升溫速度10℃/秒,700℃,5分鐘之條件正式燒結而得到PZT系強介電質薄膜。 In Comparative Example 5, the gel film obtained in the coating stage was heated to 450 ° C at a temperature increase rate of 2.5 ° C / sec in the temporary sintering stage of the temporary sintering, and the temperature was maintained for 8 minutes for temporary sintering. Then, in the main sintering stage, the film obtained in the temporary sintering stage was sintered at a temperature rising rate of 10 ° C / sec, 700 ° C for 5 minutes to obtain a PZT-based ferroelectric thin film.
在比較例6,把在塗佈階段得到的凝膠膜,在根據從前之一段暫燒結的暫燒結階段,以升溫速度50℃/秒,升溫至450℃,在此溫度保持8分鐘進行暫燒結,接著於正式燒結階段,把暫燒結階段得到的膜以升溫速度10℃/ 秒,700℃,5分鐘之條件正式燒結而得到PZT系強介電質薄膜。 In Comparative Example 6, the gel film obtained in the coating stage was heated to 450 ° C at a temperature rising rate of 50 ° C / sec in a temporary sintering stage which was temporarily sintered in the previous stage, and was temporarily sintered at this temperature for 8 minutes. Then, in the formal sintering stage, the film obtained in the temporary sintering stage is heated at a rate of 10 ° C / The PZT-based ferroelectric thin film was obtained by firing at a temperature of 700 ° C for 5 minutes.
針對實施例1~16及比較例1~6所得到的PZT系強介電質薄膜,藉由以下的手法,求出該薄膜之暫燒結後以及正式燒結後的層厚及折射率。結果顯示於表1。此外,實施例6之剖面SEM影像(倍率為10萬倍)顯示於圖4,比較例6之剖面SEM影像(倍率為10萬倍)顯示於圖5。此外,實施例6、比較例2之XRD圖譜顯示於圖6。 With respect to the PZT-based ferroelectric thin films obtained in Examples 1 to 16 and Comparative Examples 1 to 6, the layer thickness and refractive index of the film after the temporary sintering and after the main sintering were determined by the following methods. The results are shown in Table 1. Further, the cross-sectional SEM image (magnification: 100,000 times) of Example 6 is shown in Fig. 4, and the cross-sectional SEM image (magnification: 100,000 times) of Comparative Example 6 is shown in Fig. 5. Further, the XRD patterns of Example 6 and Comparative Example 2 are shown in Fig. 6.
(1)層厚測定:所得到的PZT系強介電質薄膜的層厚,藉由分光橢率計(ellipsometer)(J.A.Woollam公司製造;M-2000)進行測定,測定結果整理於表1。 (1) Measurement of layer thickness: The layer thickness of the obtained PZT-based ferroelectric thin film was measured by an ellipsometer (manufactured by J.A. Woollam Co., Ltd.; M-2000), and the measurement results are shown in Table 1.
(2)折射率測定:該薄膜之折射率,藉由同樣的分光橢率計(ellipsometer)進行測定,測定結果整理於表2。 (2) Measurement of Refractive Index: The refractive index of the film was measured by the same ellipsometer, and the results of the measurement were summarized in Table 2.
(3)剖面觀察:把該薄膜之剖面,藉由SEM(日立製作所製造;S-4300SE)所攝得之照片(倍率為10萬倍)來進行觀察。圖4為實施例6之薄膜的剖面照片,圖5為比較例6的剖面照片。 (3) Cross-sectional observation: The cross section of the film was observed by a photograph (magnification: 100,000 times) taken by SEM (manufactured by Hitachi, Ltd.; S-4300SE). 4 is a cross-sectional photograph of the film of Example 6, and FIG. 5 is a cross-sectional photograph of Comparative Example 6.
(4)結晶配向:為了調查在實施例6、比較例2所得到的PZT系強介電質薄膜的結晶配向、結晶的完成度,於圖6顯示藉由X線繞射裝置(Bruker製造;MXP- 18VAHF)製作了XRD圖。 (4) Crystallization alignment: In order to investigate the crystal alignment and crystallization completion degree of the PZT-based ferroelectric thin film obtained in Example 6 and Comparative Example 2, it is shown in Fig. 6 by an X-ray diffraction apparatus (manufactured by Bruker; MXP- 18VAHF) produced an XRD pattern.
參照表1、表2及圖4、圖5、圖6,於以下敘述評估結果。 The evaluation results are described below with reference to Tables 1, 2, and 4, 5, and 6.
考察表1的層厚之欄的數值的話,比較使用紅外線的根據二段暫燒結之實施例1~16所得到的PZT系強介電質薄膜,與不使用紅外線的根據一段暫燒結之比較例1~6所得到的PZT系強介電質薄膜的話,暫燒結後的層厚,以實施例1~16比比較例1~6更薄。這應該是根據實施例1~16之暫燒結凝膠膜之後的PZT系強介電質薄膜變得緻密的緣故。此外,暫燒結後的層厚與正式燒結後的層厚的差異,以實施例1~16比起比較例1~6還要小。這推測是實施例1~16之PZT系強介電質薄膜比起比較例1~6之薄膜在暫燒結時與正式燒結時之間熱收縮率變低的緣故,實施例1~16之PZT系強介電質薄膜比起比較例1~6更不容易發生龜裂。從而,該結果提供可以藉一次之PZT系強介電質薄膜組成物往下部電極面之1次塗佈而可以在沒有龜裂的情況下得到100nm以上的厚膜之PZT系強介電質薄膜之製造方法。 When the values of the layer thicknesses in Table 1 were examined, the PZT-based ferroelectric thin films obtained in Examples 1 to 16 according to the two-stage temporary sintering using infrared rays were compared with those of the one-time temporary sintering which did not use infrared rays. When the PZT-based ferroelectric thin film obtained in 1 to 6 was used, the layer thickness after the temporary sintering was thinner in Examples 1 to 16 than Comparative Examples 1 to 6. This should be because the PZT-based ferroelectric thin film after the temporarily sintered gel film of Examples 1 to 16 became dense. Further, the difference between the layer thickness after the temporary sintering and the layer thickness after the main sintering was smaller in Examples 1 to 16 than in Comparative Examples 1 to 6. It is presumed that the PZT-based ferroelectric thin films of Examples 1 to 16 have lower heat shrinkage rates between the temporary sintering and the main sintering than the films of Comparative Examples 1 to 6, and the PZTs of Examples 1 to 16 The ferroelectric thin film is less prone to cracking than Comparative Examples 1 to 6. Therefore, this result provides a PZT-based ferroelectric thin film which can be obtained by applying a PZT-based ferroelectric thin film composition to the lower electrode surface once and can obtain a thick film of 100 nm or more without cracking. Manufacturing method.
考察表2的折射率之欄的數值,實施例1~16比比較例1~6在全體上都較高。這應該是藉由進行二段暫燒結,提高結晶性,提高折射率所致。 The numerical values in the column of the refractive index of Table 2 were examined, and Examples 1 to 16 were higher overall than Comparative Examples 1 to 6. This should be caused by performing two-stage temporary sintering to increase crystallinity and increase the refractive index.
此外,在實施例中,關於圖3所示那樣依照二段暫燒結階段的溫度變化圖之實施例4、8及12,參照表1極表2考察其膜厚與折射率。實施例4、8及12,第1升溫速度分別為1℃/秒、2.5℃/秒、10℃/秒,而第1保持溫度為275℃,且第2升溫速度為50℃/秒,第2保持溫度為450℃。 Further, in the examples, with respect to Examples 4, 8 and 12 in accordance with the temperature change diagram of the two-stage temporary sintering stage as shown in Fig. 3, the film thickness and the refractive index were examined with reference to Table 1, Table 2. In Examples 4, 8 and 12, the first temperature increase rates were 1 ° C / sec, 2.5 ° C / sec, and 10 ° C / sec, respectively, and the first holding temperature was 275 ° C, and the second temperature increase rate was 50 ° C / sec. 2 Maintain the temperature at 450 °C.
實施例4、8及12之暫燒結後的層厚,為366nm、382nm、389nm,分別之正式燒結後的層厚為314nm、331nm、314nm;暫燒結後的層厚隨著第1升溫速度變快而有越厚的傾向,另一方面,正式燒結後的膜厚並沒有顯著的差異。此外,實施例4、8及12的暫燒結後的折射率為2.21、2.26、2.24,分別之正式燒結後的折射率為2.44、2.46、2.46;在實施例之間並沒有顯著的差異。由此結果,可知第1升溫速度即使是實施例中最快的升溫速度10℃/秒也不會產生不良情形。考慮生產效率的話,升溫速度越大越好,但是升溫速度太大的話會有龜裂的發聲等從前的問題產生,所以最好不要太大。 The layer thicknesses after the temporary sintering of Examples 4, 8 and 12 are 366 nm, 382 nm, and 389 nm, and the layer thicknesses after the main sintering are respectively 314 nm, 331 nm, and 314 nm; the layer thickness after the temporary sintering changes with the first temperature increase rate. There is a tendency to be faster and thicker. On the other hand, there is no significant difference in film thickness after formal sintering. Further, the refractive indexes after the temporary sintering of Examples 4, 8 and 12 were 2.21, 2.26, 2.24, and the refractive indices after the main sintering were 2.44, 2.46, 2.46, respectively; there was no significant difference between the examples. As a result, it was found that the first temperature increase rate did not cause a problem even if it was the fastest temperature increase rate of 10 ° C / sec in the examples. When the production efficiency is considered, the higher the heating rate, the better. However, if the heating rate is too high, there will be problems such as cracking sounds, so it is best not to be too large.
進而,參考圖4、圖5的話,由SEM的剖面照片所觀察到的PZT系強介電質薄膜(相當於圖1之參照符號12之層)可知,在實施例6所得到的PZT系強介電質薄膜明顯成為緻密的結晶構造,但在比較例6所得到的PZT系強介電質薄膜發生微小的龜裂而成為不緻密的粗的結晶構造。 Further, referring to Figs. 4 and 5, the PZT-based ferroelectric thin film (corresponding to the layer of reference numeral 12 in Fig. 1) observed by the cross-sectional photograph of the SEM shows that the PZT system obtained in Example 6 is strong. The dielectric film was a dense crystal structure. However, the PZT-based ferroelectric film obtained in Comparative Example 6 was slightly cracked and became a dense crystal structure.
此外,參照圖6的話,在實施例1~16為良好的結晶性之膜,另一方面,在比較例1~6則為無配向且結晶性低之膜。藉此可知藉由導入根據紅外線之二階段暫燒結可得緻密且結晶性高的膜。 Further, referring to Fig. 6, Examples 1 to 16 were films having good crystallinity, and in Comparative Examples 1 to 6, films having no alignment and low crystallinity were used. From this, it is understood that a film having high density and high crystallinity can be obtained by introducing a two-stage temporary sintering according to infrared rays.
由以上可知,根據本發明之使用紅外線的二階段暫燒結來製造PZT系強介電質薄膜之方法,即使一次進行塗佈、暫燒結、正式燒結出層厚100nm以上之比較厚的 層,也可以製造出沒有龜裂的緻密且結晶性佳的PZT系強介電質薄膜。 As described above, according to the method for producing a PZT-based ferroelectric thin film by two-stage temporary sintering using infrared rays according to the present invention, even if coating, temporary sintering, and sintering are performed once, a layer thickness of 100 nm or more is relatively thick. As the layer, a dense and crystalline PZT-based ferroelectric thin film having no cracks can be produced.
本發明之PZT系強介電質薄膜之製造方法,使每一層平均厚度為從前之該製造方法的5~10倍程度而進行的塗佈、暫燒結、正式燒結成為可能,適於被要求1μm~3μm的膜厚的用途,例如薄膜壓電之用途,而可以低成本提供緻密且結晶性優異的PZT系強介電質薄膜。 In the method for producing a PZT-based ferroelectric thin film of the present invention, coating, temporary sintering, and main sintering of each layer have an average thickness of 5 to 10 times that of the prior art, and are suitable for being required to be 1 μm. The use of a film thickness of ~3 μm, such as the use of thin film piezoelectric, can provide a PZT-based ferroelectric thin film which is dense and excellent in crystallinity at low cost.
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CN106518069B (en) * | 2016-09-29 | 2019-10-29 | 广东工业大学 | A kind of doped lanthanum zirconate titanate ferroelectric thick film ceramic material and preparation method thereof |
KR102380663B1 (en) | 2020-05-11 | 2022-03-29 | 김조희 | skimmer for sea water aquarium |
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JPH04259380A (en) * | 1991-02-13 | 1992-09-14 | Mitsubishi Materials Corp | Method for controlling crystalline orientation property of pzt ferroelectric body thin film |
JP4146533B2 (en) * | 1997-08-21 | 2008-09-10 | ローム株式会社 | Ferroelectric film formation solution and ferroelectric film formation method |
US6441415B1 (en) * | 1999-06-25 | 2002-08-27 | Texas Instruments Incorporated | Ferroelectric and paraelectric thin film devices using dopants which eliminate ferroelectricity |
JP2001261338A (en) | 2000-03-15 | 2001-09-26 | Mitsubishi Materials Corp | Raw material solution for forming titanium-containing metal oxide thin film, method of forming the same, and titanium-containing metal oxide thin film |
US6635497B2 (en) | 2001-12-21 | 2003-10-21 | Texas Instruments Incorporated | Methods of preventing reduction of IrOx during PZT formation by metalorganic chemical vapor deposition or other processing |
US6686236B2 (en) | 2001-12-21 | 2004-02-03 | Texas Instruments Incorporated | Methods of preventing reduction of IrOx during PZT formation by metalorganic chemical vapor deposition or other processing |
JP5013035B2 (en) * | 2003-12-11 | 2012-08-29 | セイコーエプソン株式会社 | Dielectric film manufacturing method and liquid jet head manufacturing method |
JP2009070926A (en) * | 2007-09-11 | 2009-04-02 | Tokyo Institute Of Technology | Method of forming perovskite oxide thin film, and laminate |
JP5187489B2 (en) * | 2007-09-20 | 2013-04-24 | セイコーエプソン株式会社 | Method for manufacturing actuator device and method for manufacturing liquid jet head |
JP5533622B2 (en) * | 2010-04-14 | 2014-06-25 | 三菱マテリアル株式会社 | Composition for forming ferroelectric thin film, method for forming ferroelectric thin film, and ferroelectric thin film formed by the method |
WO2011135731A1 (en) * | 2010-04-28 | 2011-11-03 | 株式会社ユーテック | Substrate processing apparatus and method for manufacturing thin film |
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TWI650774B (en) * | 2014-03-27 | 2019-02-11 | 日商三菱綜合材料股份有限公司 | PZT-based piezoelectric film forming composition doped with Mn and PZT-based piezoelectric film doped with Mn |
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EP2645441A3 (en) | 2015-01-28 |
CN103359785A (en) | 2013-10-23 |
EP2645441A2 (en) | 2013-10-02 |
TWI586628B (en) | 2017-06-11 |
KR20130111304A (en) | 2013-10-10 |
JP2013211306A (en) | 2013-10-10 |
EP2645441B1 (en) | 2016-12-14 |
US20130260142A1 (en) | 2013-10-03 |
JP5919956B2 (en) | 2016-05-18 |
KR101934124B1 (en) | 2018-12-31 |
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